Subresinous esterification derivatives of hydroxylated amides and method of making same



invention'td provid ra This invention relates to a. new chem-icall-prod- J f -fmefniairt 'object-1 of our invention is to provide #motherobit-of our invepttomsto povide a Ipiatticable' methodfofifr'narmlfactur'ingsaid postiontof Iattel that forcrude oil eiiius'ov composition ofmatterfis adapted for indicated.`

polybasiecarboxyfacid 'Iiavirgfnt over'eight' cal" bonatoms, andJin'such-a saidV acidic material'ofinteriediate 'product Awith at'-vlealsti'ney "mole'fof, an alcoholic compound.' of

compositions of yrnatterwhich 'have'- titiltydny various'lfarts,andfpart cation'. of `cradle oil; y Y Y l "Ilfie compoundsherincoiitemplatedmay lbe pfdce'd inem. Siiibalem infer..buttarertsually 1 manufactured by followin "one of "two 'generalvproductgwhich, in tiitnyisjraoteyd .withjan 'a1-t colii'c bodyl ofv thekindliereiiafter described; and nd'om'entar'ily'"indcatetby the formula;R1(OH)m. Genericali thealcoholie body here-"45 "We have discovered Ithatif'A one'loxyalkylates glycerol so' as'to introduce t1east`three oxyy yfanne'r as ftq'yieid ar fractional esterfdueftoth 'presence'of fat leastZPATEENT l offrit,cia y y t tion-Augusta 194s, serial Ndyi'omtfg ,y y

` io Claims; `(C1. 26o-54m?.

in whichthe value of 1i nai" vrj from 3 to 10 and al1 'the rlie's' of nneed notebe identical.

Ifa polybasic. carboxy acid-be indicated by thel formula: f Y

` Coon "icoon: coca carboxy; acid may be indicated by*` the.- followingintwmcifn" tiievalueH-of--onefor ttfo. simiindicated by-r4 the fol-'H1531 ,y

(ctrnotfooomoo-omt" @immobili I empl() 55Eiy'fde'scribedlin'atgenen-sesfasador-15 ther-i obviously, one'may obtainamaterial of the type indicated by the following formula:

in which :c is 0, 1, or 2, y is 0,691 or12, and a isl, 2' or 3, andzcisOor 1, andy islor 2.

It has been previously statedthat. compoundsof the type hereincontemplated maybe `ob-H` tained by oxyalkylating agentsgwithout Abeingunder suitable conditions, instead of obtaining the monomeric compoundsindicated, one would, 1n reality, obtain a polymer in the sense, forexample, that polyethylene glycols represent a polymer ofethyleneglycol. The term polar is frequently used tol indicate thepolymerized product derived from a monomer in which the polymer has thesame identical composition as the monomer. `In the present instance,however, polymerization involves the splitting and loss of water so thatthe process is essentially selfesterification. Thus, strictly speaking,the polylmerio compounds are not absolutely isomers of the monomericcompounds, but since, for all practical purposes, they can be soindicated, and since such practice is common in the arts concerned withmaterials of this type, it is so not included, strictly speaking,"^bythe unitary" t in 'which n replacesthe numbers 2,V 3cr 4, `z includesthe acidic hydrogen atom itself. :Inl-the above formula, and hereafterfor convenience, R1 is intended to include any hydroxyl groups thatremain.

If the compounds herein contemplated are obtained under usualconditions, atV the lowest temperato "thenjthe' monomeric form is moetTh`e"pr'd1'iction` ofthe compounds herein con-l.' templated is theresult of one or more esterication steps. 4Asis well known,esterification procedures can be carriediout in Various manners, butgenerally speaking, esterications can be carried out at thelowestfeasible temperatures by .usineA one 9r.-..f evera1 procedures. fOne pro- Cedure is' to pasean inert@ledges.ihrouehlfh v mass. to beesteriet and. .have present et. the same time a small amount ofapatalysgtsuch as dried HC1 gas, a dried sulfonic acid, orV the like.Anotherand better procedure, in many instances, is tomemployr thewvaporsof a suitable liquid, so as 'tdre'mv'e any Water formed and condenseboth the vapors of the `liquid employed and the water in such a manneras to trap out thefw'ater and-return theliq'uidfto the reactingvessel-zA "'-I'his--procedure is 'commonly' employedy in the arts, andfor convenience;v reference `1s made to U. S. YPatent No. 2,264,759,dated December 2, '1941, to Paul C. Jones.

Referring again to the last two formulas indicating the Ecompoundsunderr consideration, it can b-e readily understood that such compounds,in numerous instances. .have thepropertmf polyfunetiorialitw vewfofthiS-,-,fe;ci, ,wherethere leest 01,16. @residual QarbeylAv and. at,least l residual hydroxyl, .wouldixpect that.;

adopted here. Thus, reference in the appended claims to polymers isintended to include the self-esterication products of the monomericcompounds. I

In view of what has been said, and in view of the recognized hydrophileproperties of 4the recurring oxyalkylene linkages, particularly theoxyethylene linkage, it isapparent that the materials hereincontemplated mayyary from compounds which are clearlyvwater-soluble,through self-emulsifying oils, to materials .which arebalsam-like and sub-resinousor vsemi-resinous in nature. Thecompoundsmayyaryffrom mono- 'mers to polymers, inv which the unitarystructure appears a numberof times, for instance, 10 or 12 times. It, isto `be noted that true resins, i. e., truly insoluble `materials of ahard plastic nature,vare vnotherein included. In other words,thepolymerized compounds are soluble to a fairly definite extent, [f orinstancevat least 5% in some solvents, such aswater, alcohol, benzene,dichloroethyl ether, acetone,.cresylic acid, acetic acid, ethyl acetate,dioxane, or the like. `This is simply'another way oflstatingy that thepolymerized product contemplated must be of the sub-resinous type,rwhich is commonlyreferred toas an A'resin, or a B resin, asdistinguished from a C resin, Whichrisy ka. highly infusible, insolubleresin (see Ellis, Chemistry of Synthetic Resins (1935), pages 862, etyseq.). l

Reviewing `the `form `as presented, it is obvious that one may obtaincompound'swithin the scope disclosed, which contain neither a freehydroxyl nor a freel carboxyl group, and one may alsoI obtain acompoundofthe type in which there is presentv at4 least one free carboxyl, or atleast one free hydroxyl, or both. The-word polar has sometimes been usedin the arts in this particular sense to indicate the prsence of at leastone free hydroxyl group, or at least, one free carboxyl group, or both.In the case. ,ofI the free carboxyl group, the carboxylic hydrogen atommay', of course, be replaced byV any'ioniz'able hydrogen atomequivalent, such, for'exam'ple, as a metal, an varrimoriiurn radical, .asubstituted ammonium radical, etc. `In lthe hereto appended claims theword fpoflar is .used in this specific sense. I

We are aware that compoundssimilar to those contemplated inthe present`instance may be derived from polyhydroxylated compounds having morethan three hydroxyl" groups. AFor instance, ythey may be derived fromacyclic diglycerol, triglycerol, tetraglycerol,.mixed polyglycerols,mannitol, sorbitol, various vvhexitols, dulcitol, pentaerythritol,sorbitan, mannitan, dipentaerythritol monoether, and other similar com-.lpounds. Such particular types in which higher hydroxyflatedy=materials are subiected l -to"-` .oxyalkylationandl'thentemployedrinthesame 'manner as oxyalkyla'ted glycerol,ls'lemployed inthe pres-5l ent instance, are not contemplated'in-thisspeciflc Vcase,ialthoughlfattention His" directed tofthe Same :a '5;.f-5I Reference yisalsofmadev to other! oxyalkylated compounds which l rmaybe E used; as reactants` .to` replaceoxyalkylated;lv iglycerol,- f or"oxyalkylated ethylene "-glycoL'fV whchilatte'r l reactanty is .':de,

. scribed! inan f application hereinafterlreferre'd. to,

those having'V more than three Ahydroxyl groups.v

' tetrahydroxylated ethylene diamine, etc.: ,Corn` pounds `'may alsoxbederivedfromcyclic-diglyc- Furthermore', forA convenienceJ-attention isydifl rested '-toa. somewhat 'similar class of `materials y which aredescribed in our application ,Ei'erial'f'y No.

4d13-8l','-ledf July "Ty/1941,'-1Which subsequently matured-ast1U.S:^PatentxNo. 2,324,493, dated July Said application involves the useof the same type of alcoholic' bodiesfor reactants, but

is limited, among other thngsto the compounds whichv are essentially;symmetrical in nature, for instance, involving thejntroduction of twoalcoholic residues, whereas, inthe present instance,

one, two, or three, or more, might be introduced.

As vindicated previously,y the polybasic acids employed are limitedv,tothe type having not morethan`eight carbon atoms, for example, oxalicmalonie; sueci-nic, ig-lutaric, `adipic,` maled-and phthalic. Similarly,onemay employ acidssueh producey resinous materials, i andgreater care'Amust beemplfoyed if the'ultmate or final product y be of a sub-resinoustype.`V` Specifically, the preferred type of polylas'icfaidis such as tocontain sixrcarb'onjatoms or-lesss Generallysp'eaking.,.the. higher;fthe-:temperature employed,l the as-fuma'rio, -g-lutaconic', and variousothers, such f as citric, malicftartaric, and the likes' rThe selec--tionlof the particular"tribasicror diba'sic acidjvTheysamre,procedure?islfollowed fas in the two previousexamples, exceptthat thefat'ioy of ethyl-'lj cassiera/it,ishtocbtainy large yields ofesteed product, although:polymerization may be stint-'- ulated.A .Qxalicacid maym .be 'comparatively cheapLhutit decomposes readily atv slightlyabove the boiling point ofwater.. -For. this reasomit is:l v moredesirahlefo usev anacid which, ismore re-- sistkant,topyrolysis.,lSimilarlmiwhen a polybasic' acidis available, in. theA formofrianyanhydridaV parati'vely low'onalper molar has such! anhydride is apttofproduce the ester with greater" ease ythan ,the'hacid1 itselfl'rforthisv reason.1 maleicl, ,anhyd 'de 4 is Vp2p rticularly adaptable, and:Y, also,everythingV else consideredgt e cost is com-f -fever though.somewhat Alii'glyier on a.per, pound-basis. Suce;

refer to the use of maleic anhydride, although it is-understood that anyother' suitable polybasic -acid mayv be"empl'feda Furthermore, referenceAs far1 as the rangeof yoxyethylatedA glycerols employed as reactants isconcerned, it is our preference to employ those'in'which approximately15 to 2e yoxyethylene groups hayebeen introduced into.. a sineleelyerolmolecule, Thismeanslthat approximately five t0 ,eight oxyethyleneradicals have been introduced .for each original.y hydroxyl. group. f ll The oxyalkyltion'of glycerol isa Well-known procedure (see Example 1 1of vGerman Patent No. 605,973, datedNovember 22, 1934, to I. G.Farbenindustrie G). `The procedureindicated inthe following -threeexamples is substantially identi# cal 'withfthat outlined insaid-aforementioned German patent.

Y l OxyErHYLATED GLYCEROL- v.

llnounds of glycerol are mixed with 1/2%., by`

weight, ofcaustic soda' solution having a specific'l gravity; of 1.333.The Causticsoda .acts .as a1 Catalyst@ The ethylene; oxide is; added`iny -1 relacooled alseond. small, portion, 1 for instance, 44

more, Y pounds; of ethylene loxidm are 'added andtneprocedurerepeated.until the desired, raue ef- 1 5 pound; moles of;:ethylene 1 ,oxi&:1e-;.toy oneA pound:k niolaof; glycerol "is-.obtainedThiszrepresents: v66oV pounds of ethylene oxide for 92pounds ofglyce ermy 1 j 1 f i f :4

"- 11 |`O'mirramarsa GLYcERon .a

Example;

The frane of ethylene oxide isi 'increasedA te e1' pound. moles f foreach poundrjmole-fof glycerol. Othermse, the same procedure` is.followed.. as-in Example 1, preceding... ,1; 1 gir; v, .i1 v1 ene oxidetot glycerol is increasedtoil to j -xyETHY'LATED .GLvoERoL'MAnnA-Tni1*.'(Dnel pound mole of oxyethylatd glycerol '(lfi'n'iy 1 5.vl ratio):prepared in'themanner' previously de# scribed'is treatedwith one poundmole Vof ma'Ieic anhydride and heated. aty approximately 11o@ cui forapproximately 30` min1;`ite'sf"to'2hourswwvitliv constant-"stirring,sofas-to yield-av monornaleatel The .Seme procedure followed as in ilbrei bulk of the examples,ihereinafterillustrated, will oxYsrHYLAi-EnGLYcERox. MALEATE Example 3 OxYE'rHYLA'rED GLYCEROL MALEATE Example 4The same procedure is employed as in the preceding examples, except thatoxyethylated glycerol (ratio 1 `to 18) is substituted in place ofoxyethylated glycerol (ratio 1 to 15).

QXYETHYLATED GLYcERoL MALEATE Example 5 The same procedure is employedas in the preceding examples, except that oxyethylated glycerol (ratio 1to 21) is employed instead of oxyethylated glycerol (ratio 1 to 15) `or(1 to 18).

Previous reference has been made to an alcoholic body which has beendefined-generically by the formula R1(OII)m. The sub-generic class ofalcoholic compounds employed as reactants in the manufacture of thepresent compounds, are hydroxylated acylated amides containing (a) anamino nitrogen-linked acyl radical derived from a monocarboxy acidhaving not more than 5 carbon atoms; (b) an acyl radical derived from adetergent-forming monocarboxy acid having vat least 8 and not more than32 carbon atoms; and (c) an alcoholiform hydroxyl radical.

Detergent-forming acids having at least 8 and not more than 32 carbonatoms are exemplified by fatty acids, naphthenic acids, abietio acids,oxidized paraiin or wax acids, or the like, or by simple modicationsthereof which do not detract from the ability of the acid to combinewith alkali to produce soap or soap-likematerials. As to oxidizedpetroleum acids, see U. S. Patent No. 2,242,837, datedMay 20, 1941, toshields.

Thus, hydrogenated oleic acid, chlorinated naphthenic acid, orbrominated abieticA acid will form such detergent-forming bodies withthe same ease as the parent materials themselves.

. The oxidized acids obtained yby blowing or oxidation of the acidsoresters, are satisfactory. Such acids have frequently been referred tocollectively in the art as monocarboxy detergentforming acids. Needlessto say,` the acylation need not be conductedby means of the acid itself,but may be conducted by means of any compound of the acid which containsthe acid radical; for,

instance, an ester, an amide, an anhydride, `an acylchloride, etc. v

It is our preference to use the fatty acids as the most desirable formof a detergent-forming acid, and particularly the unsaturated fattyacids, for instance, ricinoleic acid, oleic acid, mixed fatty acidsderived from soyabean oil, rapeseed oil, sesame oil, cottonseed oil,corn oil,l peanut oil, and thellike. Fatty acids, such as lauric acid,myristic acid, palmitic acid, and the like, `may beemployed. o

The low molal monocarboxy acids having not more than ve carbon atoms areexemplified by acetic acid, formic acid, lactic acid, propionic acid,butyric acid, vhydroxybutyric acid, furoic acid, etc. y

In regard to both the detergent-forming acids and in regard to the lowmolal acids, it is obvious that loney need not use the acid itself as areactant, but may usev some suitable derivative,

such as the acyl chloride, the anhydride, the ester, or amide; `i. e.,any suitable' form may be used which is the functional equivalent insupplying the acyl radical; Suitable primary and secondary amines whichmay be used as primary reactants include the following hydroxylatedtypes: Diethanolamine, monoethanolamine, ethyl ethanolamine, methylethanolamine, propanolamine, dipropanolamine, propyl propanolamine, etc.Other examples includey cyc1ohexylolamine, dicyclohexylol-amine,cyclohexyl ethanolarnine, cyclohexyl propanolamine, benzylethanolamine,Vbenzylpropanolamine, pentanolamine, hexanolamine, octylethanolamine,octadecylethanolamine, cyclohexanolethanolamine, etc. v

If vthe low molal monocarboxy acid happens to be hydroxylated, asin theinstance of glycolic acid', lactic acid hydroxybutyric acid, and thelikeit isobvious that a hydroxylated detergentforming acid, forinstance, ricinoleic acid, hydroxystearic acid, and the like, could beesteried therewith, i. e., with the hydroxyl group,which is part;of thelow molal acyl radical; and. under such circumstances, the primary' orsecondary amine need not be hydroxylated- `Under these circumstances,one might. employ compounds such as amylamine, diamylamine, butylamine,dibutylamine, benzylamine, cyclohexylamine, etc.

4Other suitable typesof amines willbe describedsubsequently. Forinstance, one may employ the type involving the presenceof Aan etherlinkage, as, for example, the following:

CnHiOCiHiOH lHN '\C5H4OC2H4H 01H40 Carnon HN '\C2H4OH Y Hg'NciHiommoHvSubsequently, Vreference will be lmade to U. S.

- Patent No.-2,238,929, dated April 22, 1941, to

Cahn and Harris. Momentarily,attentionisdirected to the numerous aminocompounds, particularly secondary hydroxylated amines there described.Such additional amino compounds are suitable as reactants, in viewofwhat will be said subsequently. l

Example A, part 1, of the vaforementioned Cahn and Harris patent willserve excellently as an initial illustration and is as follows:

Example A (l) 224 grams of methyl acetate (3 moles) and 210* grams ofdiethanolamine (2 -moles) were mixed together, two layers forming atrst, the mixture becoming a homogeneous mass after a short time. Themixture was refluxed for 19 hours, at which time of the diethanolaminehadreacted. A portion of the reaction mixture was subjected to a vacuumof 6 millimeters at 60 degrees C. in order to drive olf the volatilematerial, namely, the unreacted methyl, acetate and the. methyl alcoholwhich was formed during the reaction. The residue, upon titration,showed a content of 4.64% of free' diethanolamine. To 192.5 gramsof thisresidue, 34.7 gramsfof methyl acetate were added and the mixture wasreiluxed for 31/2`j hours.v The `resulting reaction product was thenfreed from its low boiling constituents, namely, the methyl alcohol andunreacted methyl acetate, by maintaining the'mass bythe,.fllowingrjformula:

v aaa-i557? at '70 deereesnC. undcnmafpressurefuf'Gimilliacompound whichwas Vessentiallythe vacetic acid amitie. @die qiethanolaiiina-hng ,thefollowingformula: v y

. described, it yis obvious that one: canftheii esteri@ the materialwith yeitherv one ortwof-xnoles'ofa detergentlforming" menecarboxyvacidi; 1 so "as f to Obtain al hydrolylatedyderiyativc. ff; Qlfwiusly.`if. the detergent-forming` acid employed does not contain an alcoholichydroxyl `radical,4 for in- Stance/, ii it isof the type other than-thatexemplified. by ricinoleic acid. .hydrcxfysteario acid;

and the. like, then one can. esteriy one. mole 'Oifsuch'dotergentformins acid with ai .compound of the kind. above described..forth@ reason that there must locl a residual aleoholifornr rdroio'lradical.- ,Igfzifhoweyeryaa acid such as ricinoleic acid, hydroxystearicacid,r or thevlike, is .emplbyedf then, of @oursatwoirioles of Suchdetergentiormin'g acidcanbeemployed. Similarly, if desired, onemishtesterify one hydroxyl with. oleicacid. andi menthe: hydmxylmdthricirioleic acid.)

, If the experiment alici/'e described .ilsvreneatedlusing'monoethanclandne .in the equivalent amount. ythen the' lined. product 1S`Clilar'ilcteii'zed,

f Gema-'2"' cHi-.C-Nf

The limitations'in regardto the aboye type of compound isperfectlyobvious.` Unlessionecan produce a' secondary 'aniiifden'` whichis- "diillcult',

, yand generally speaking, "not i'p'articiilarly'*reas ible, 'one must,offnecessitwesterlfy with a' hyi I droxyl'ated' `detergentdorming` acid,s'ueh as ricinoleic acid, hydroxyfstearic acidf, or the like'.

additional opportarlityv Vior reaction- .and-fgrtner elaboration is,not, necessary, excam; Pomona-.to

. point outthat even atype'- Q1? material siichfas the following; i i

y mishaps employed. pmviieii that .riein'oieie acid,

forex-ample; is:csteriedfwiththevv hydroxyl of the" W: molalimonocarboxyf; acidvacylv group'. Other, variants todjnumerous; to'mention `sindL ,Slthemsewg as; for iexampl'e, .derivatives of i` 60 7The presence of this additional hydroxy ofte-rs tris (hydroxymethrlxannomethanefor simi1ar types; offfcompoundsafsuchias an amidecftthe vfollowing type Which mayheiusedior reaction with adetergent-formingacid:

Attention is directed to the aforementioned. Cahn-facer.Harris'iratentir,1.Sfifiir.-v waait-.illustrates a largenumpefof 'nterrnediateproductswhich ymay be utilizdtproduce various rfinal 2Q ccmoositiors oli-matter.asfor,e2 ari1plecurated @rsulfoaatedf derivatires. @contemplated- .inSai@ aforementioned U. S. Patent No. 2,238,923.;I

obviously-can used: as-alcoholic bodies'firi' the preparation ofcompounds :ofrthe type herein con- 122.Illi@litsC1. llchmaterialsasthere describedare ,lagged derivatives i1 1 hier slated seco "amairlines; but for the A'piioses"hereln plated, such limitation does notexist,"'in View ro what `hasfalready beensaidj.: f 'i fc-uitrit'.

Byway of illustration,y the` following examples .will Serve:

is reacted with one moleof 'ricinlei until esterica'tn is complteff Suchesteriiication reaction can pefcoriducted by any one of theconyentionalmeans. usiially heating at a temperature above-` the' boiling'pointofWateijvfor instance, 11d-'1609* "i i it 'may'f'be desira'b l throughtl'ifie'reja'oting?Y mass; as,v -for xa'rri' l carbon dioxide or d'ied'friitrogenfff'Sometimesthe reactionk is* extended bythe-presenceofa all amunt'ff' a``sl1l1f0ifait-.tidVV s'taneei'q/Oftol'enefsl iristances,r esterication mayi be conducted-1rithepresence'ofaninertfsolyent, such as Xylerie'l which is'fpei' ittedjto'distilfofecarrying-'water vapor they water' is diverted to af'Ysuitable dfrawloff fc'oii- Alvin?` *Eamplegz 51.0 grams 2 moles) oftheabeti@y aci l'amide of diethano1amine,1producedr .asa described; in party1 hereof, and 38.0 grams (lv I nole) of lauric acid were heatedtogether for lininutes at approximately' 200 C.; While. passing;v carbomdioxide'gas through the reactionmixture. vAty the 'end 'ofthe 15minutes; the -ffre'el .-lauric acid had; decreased to. 1.3%. 'IhApro'dictxwasi aQy'elloWl colred syrup dispersible Water?fandvyligiyirrg;y goed*."i-o'amirligA properties. It could be salted out ofitslsoliuti'on Amm?? lltabl @Wmateriaiismoxmglyeryli the xylenereturnedtothe-reacting'- vesseiWii-iie i bythe addition thereto of sodiumchloride." The product consisted essentially of'a compound having thefollowing formula:

C2H4OH ona-C-N O CzH4-0-( J-C11H2a The above directions arevsubstantially asthey appear in part 2 of Example A in theaforementioned Cahn and Harris patent. Previously,v reference has beenmade to the same patent in regard tothe manufacture of the acetic acidamideof diethanolamine, referred tO as Part l hereof in the foregoing.

j HYnROxYLArEn AMIDE T YPE IN'rERMEDiArE l Emample The same procedure isfollowed asin Example 2, except that ricinoleic acid is substituted forlauric acid. i

, HYDROXYLATED AMIDE TYPEINTERMEDIATE Example 6 mima- The acetic acidamide of tris (hydroxyethyl) aminomethane, previously described, issubstituted for the acetic acid-amide of diethanolamine, in Examples 2-5preceding..

COMPLETED, MONOMERIC DEEIVATIVE f y Ewample'l t Y l One pound moleof `a-productf of the kind fro described under the heading ,Oxyethylated Iglycerol maleate, Example l is reacted withL one pound mole of"Hydroxylated amidetypefintermediate, Example 3, preferably inthewabsence p of any high boiling hydrocarbon or inert solvent. However,if an inert vaporizing` solvent is` employed, it is generally necessaryto use. one which has a higher boiling range than xylene, and sometimesAremoval Of such solvent might present a t' COMPLETED MONOMERICDERIvArIvE Example. 2y

The same procedure is followed as j inf'Completed monomeric derivative,`Example 1, preceding, except that the dimaleate; described under theheading O'xyethylated glycerol maleate, Example 2 is used instead of themonomaleate. A

'' -COMPLErEnf-MONOMEEIC DERIvArrvE Emble f `Thesame `procedure. fis-followed .asA in the two preceding examples, ,except thatv the:trimaleate isA substituted for the monomaleatefor dimaleate in-the twopreceding-examples.

' "COMPLETED MONOMEEIO D ERivgirIvE Ef'vample 4L' The same procedure isfollowed as in Examples 2- and 3, immediately preceding, except that foreach poundmole of the maleate, or each pound 'molemf the -trimaleatainsteadof .using one-pound mole of4 hydroxylated esterV amide of the.kindemployed i-n .Examples '1 to v3, preceding, as a reactant, one,employsv two poundV moles.

- COMPLETED MONOMEE'rc`DEEiveTIvE Example 5 rThe same `procedure isfollowed as in Example3, preceding', except that for 'each' pound moleof trimaleate,' instead of adding'one pound mole of f hydroxylated'ester amide Of 'the kind employed in Examp1e-sf1"-to3, preceding, oneadds three""fpo1.ind` moles'" Of t'hydroxylated esteramcle ofthekindllemployed"inExamples` l' to 3 for reaction, v y

COMPLETED MoN'oM-Enrc DERrvsrIvE l "E:1:a,17t plef6*4 Reference to theprecdingexamples will show that in each and every instance oxyethylatedglycerolj ratio l to la), has'l Abeen 4employed as a1 raw' materialonprimary'reactann Iny the .pre-sent instance, a morehighly[Oxy'ei-,hylalted 'glycerol is employed, to wit, one involvingrthe'ratio of 1 to 18. (See"Oxyethylated glycerol maleate, Example 4,precedingJ" COMPLETED MONOMEEIC DERIVATIVE Ew'mple 7.' Thefsameprocedurek is followedfaszin Example 6,.immediatelyfpreceding, exceptthatthe Oxyethylateclglycerol. employed;y represents one having any evenhigher degree -Of oxyethylation. For example, one indicated-by the ratioof- 1 to 2l.

-(See ,Oxyethylatedlglycerol maleate, Example 5,

preceding.-)-- ya; COMPEETEEMONOMEEIO DERIvArIvE 4 ,.Eammzlle 8 The sameprocedure i-s followed as in Examples 1 to 7, preceding, except thatinstead Of employing a reactant of the kind described under the headingHydroxylated amide type intermediate, Example 3, onev employsr instead areactant of the kind ydescribed under the heading -Iydroxylateol amidotype intermediate, Exampe..6 sy w''j".' m 'l l The methoaof'producmg'such fr'atioai estersis well known'. The' generalprocedure is to employa" ten'iperature above the boiling point `of waterand be1ow the pyrolymcpint of the reactants. The'vproducts are mixed and stirred constantlyduring the heating land estercation step. If desired, an inert gas, suchas dried nitrogen Or dried'carbon dioxide, may be passed through? ythe'-mixture.r Sometimes it' is desirable to add-,aniesteriiicationf`catalyst, suchy asv sulfuric; acid,1b'enzene sulfonicacidjor the like.'Ihis is thegsame general procedure as employed inthe:manufactureofzethylene' glycol' dihydrogen COMPLETED POLYMERICDERIVATIVES INCLUDING HEAT-REARRANGED COGEN ERS f Example 3 The sameprocedure'is followed as in, Examples l to 2,?preceding, except thatthekpolyfunctional monomer is selected from the kind described under`the heading Completed monomeric derivative, Example 8, instead of'fromExample 7.

l COMPLETED POLYMERIC DEiuvA'rIvEs INCLUDING HEAr-REARRANGED CoGENERsExample 4 ized product need not be obtained as a result of a two-stepprocedure. Ing'other words, one need not convert the reactantsintothemo'nomer and then subsequently convert the monomer into thepolymer. The reactants may be converted through the monomer to thepolymer' in one step. Indeed, the formation of the monomer andpolymerization may take placesimultaneously. This is especially true ifpolymerization is'conductedin the absence of a liquid such as xylene, aspreviously described,` and if'one uses a comparatively highertemperature, for instance, approximately 220 C. for polymerization.Thus, onev pound mole of an oxyethylated glycerol polymaleate is-reactedwith one mole of a material of the kind described runder theheading Hydroxylated amide type intermediataExampleB.' for approximatelyhours ata temperature of about 220 C. until the mass is homogeneous. Itis stirred constantly during reaction. Polyfunctionality `may reside inYdehydration (etherization) vof, tWo hydroxyl groups attached todissimilar molecules.

The fact that the polymerized and heat-rearranged products canlbe` madein asingle step,

agents in the laundry, textile, and dyeing industry; as wetting agentsand detergents in the acid washing of fruit, in theacid washing ofbuilding stone and brick; as a wetting agent and spreader intheapplication of asphalt in road building and the like, as aconstituentlof soldering ux preparations; as a notation reagent in theiiotation separation of various minerals; for occulationl andcoagulation of various aqueous suspensions containing negativelychargedparticles such as sewage, coal washing Waste water, and varioustrade Wastes and the'like; as germicides, insecticides,` emulsiers" forcosmetics, spray oils, water-repellent textile finish, etc. These usesare by no means exhaustive.

.However, the most important phase" of the present invention, as far asindustrial application goes, is concerned with the use'of'the materialspreviouslydescribed as demulsiiiers for waterin-oil emulsions, and morespecifically, emulsions of water or brine incrude petroleum;

illustrates a phenomenon which `sometimes occurs either in suchinstances where alcoholic bodies of the kindherein'illustrated arecontemplated as reactants, or where somewhat kindred alcoholic bodiesare employed. The reactants may be mixed mechanically to give ahomogeneous mixture, 'or if thereactants do not mix to giveahomogeneous-mixture, then early in the reaction stage there -isformed'to a greater or lesser degree, suicient monomeric materials v-sothata homogeneous system is present. Subsequently, as reactioncontinues,the system may become heterogeneous and existin two distinct phases, onebeing possibly an oily body of moderate viscosity, and the other. beinga heavier material, which is sticky or sub-resinous in nature. In manyinstances, it will be,v found that the thinner liquid material is amonomer and the more viscous or resinous material is a polymer, aspreviously described. Such product can be used for demulsication byadding a solvent which will mutually `dissolve the two materials, orelse, by separating the two heterogeneous phases and employing each asif it were a separate product ofreaction. i

Materials of the kind hereinfcontemplated may find uses as wetting,detergent, and leveling We have found that the particular chemicalcompounds herein described may alsobe used for other purposes, forinstance, as a break inducer iny doctor treatment of the kind intendedto sweeten gasoline. (See U. S. 'Patent No. 2,157,- 223, dated May 9,1939, to' Sutton.)v

Chemical compoundsfof the kind herein described are also of value assurface tension depressants in the acidization of `calcareous oilbearingstrata by means of strong mineral acid, such as hydrochloric acid.Similarly, some members are eiective as surface tension depressants orwetting agents in the flooding of exhausted oil-bearing strata.

As to using compounds of the kind herein described as'flooding agentsfor recovering oil from subterranean strata, reference is made to theprocedure described in detail in U. S. Patent No. 2,226,119, datedDecember 24, `1940, to De Groote and Keiser. Y As to using compounds ofthe kind herein described as demulsiers, or in particular as surfacetension depressants in combination with mineral acid'or acidization ofoil-bearing strata, reference vis made to U. S. Patent No. 2,233,383,dated February 25, 1941, to De Groote and Keiser.

Cognizance must be taken of the fact thatthe surface of the reactingvessel may increase or decrease reaction rate and degreeAofpolymerization, lfor instance,` an iron reaction 'vessel speeds upreaction and polymerizatiom'compared with `a glass-lined` vessel.

yAs, has been previously indicated, the sub-genus employed as an alcoholin the present instance 1s one ofA a series of alcoholic compounds whichare contemplated in our co-pending applications `Serial NOS. 497,118,497,119, 497,120, 497,121, 497,-

and 497,135, all filed August 2, 1943.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patentis: fr

in which RCO is the acyl radical of a monocarboxy-acid having not over5l carbon atoms; R400 is the acyl radical of a Adetergent-formingmonocarboxy acid having at least 8 and not more than 32 carbon atoms;R-Ois a memberof the class consisting of ethylene oxide radicals,propylene oxide radicals, butylene oxide radicals,

and glycid radicals; vRe is a hydrocarbon radical containing not over 18carbon atoms; n isa small v whole number not over m is a numeral varyingfrom 1 to 2, m is a numeral Varying from O toy 1, and m" is a numeralvarying from 0 to l; with the proviso that m+m|m"'=2'; .the acyl groupsubstituted4 for a reactive hydroxyl-hydrogen atom of said hydroxylatedamide, being the acyl radical of an acidic fractional ester of theformula:

in which -OCRiCO- is the acyl radical of aV polycarboxy acid having notover 8 carbon atoms;

Z represents ametallic cationiRr-O is a member of lthe class consistingof ethylene oxide radicals, proplene oxide radicals, butylene oxideradicals, and glycid radicals, and n represents a numeral varying from 3to 10, and 11," represents 'a numeral varyingfromO to 2, Yand frz/'frepresents -a numeral varying from 1 to 3, with the proviso that the sumof n+n"=3.

2. The ester of claim 1, wherein m is 0. 1 3. The ester of claim 1,wherein m is 0, and R4CO -is a higher fatty acid having 18 carbon atoms.v

4. The ester of claim 1, wherein m" is 0, and R400 is ahigherunsaturated fatty acid.

n 5. The ester of claim 1, wherein m" is .0, R4CO is a higherunsaturated fatty acid, and R is an ethylene radical.

6. The ester of claim 1, wherein m" is 0, RiCO l is a higher unsaturatedfatty acid, R is an ethylene radical and the polycarboxy acid isdicarboxy.

7. The esterof claim 1, wherein mis 0, RiCO is a higher unsaturatedfatty acid, R is an ethylene radical, and -OCRiCO- is a maleic acidradical. v

8. The ester of claim 1,wherein m" is 0, R4CO 5 is 4a higher unsaturatedfatty acid, R is anv ethylene radical, and -OCRlCO- is a phthalic acidradical. o

9. The ester of claim 1, wherein m" is 0, R-iCO is a higher unsaturatedfatty acid, R is an ethylene radical, and --OCRiCO- is an adipic acidradical.

` 10. The method of manufacturing esters depropylene oxide. radicals,butylene oxide radi-cals,

and glycid radicals; R3 is a hydrocarbon radical containing not over 18carbon atoms; n is a small whole number not over 5; m is a numeralrvarying from l to2,y m is a numeral varying from 0 to 1, and m is anumeral varying vfrom 0 to 1; with the proviso that m-|-m+m"=2;

yWith an acidic fractional ester of the formula:

,polycarboxy acid having `not over 8 rcarbon atoms; Z yrepresents ametallic cation; R-O is a member of the class consisting Iof ethyleneoxide radicals, propylene oxide radicals, butylene oxide radicals, andglycid radicals, and n represents a numeral varying from 3 to 10,'andn". represents a numeral varying from O to 2, and 11.*" represents -anumeral varyingl from 1. to 3,

MELvIN DE GROOTE. BERNHARD Karst-m.

